Selective hydrogenation of oxoprocess aldehydes



Nov. 3, 1953 D. E. BURNEY Er Al. 2,658,083

SELECTIVE HYDROGENATION OF OXO-PROCESS ALDEHYDES Filed April 26, 1951 2Sheets-Sheet l Product Dona/d E Burney Wil/iam J. Cerveny TTOIPA/EY2,658,083 SELECTIVE HYDROGENATION OF OXO-PROCESS ALDEHYDES Filed April26 1951 Nov. 3, 1953 D. E. BURNEY Er AL 2 Sheets-Sheet 2 vm Bi INVENTORSgasp?.

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Patented Nov. 3, 1953 SELECTIVE HYDROGENATION TOF OXO- PROCESS ALDEHYDESDonald E. Burney, Griffith, Ind., and William J. Cerveny,fLansing, Ill.,assignors to Standard Oil Company, Indiana Chicago, Ill., a corporationof Application April 26, 1951, Serial No. 223,124

10 Claims.

Our invention relates to the selective hydrogenation of carbonyl groupsin the presence of olenic double bonds. More particularly, it relates tothe conversion of carbonyl compounds into alcohols in the presence ofoleiinic compounds without simultaneously effecting the saturation ofthe olenic linkages in said olenic compounds.

Numerous attempts have been made in the past to convert organiccompounds containing carbonyl groups into the corresponding alcohols byhydrogenation, without simultaneously saturating oleiinic double bondspresent in the charging stock, either in the same compound with thecarbonyl groups, or in different compounds. For example, Adkins(Reactions oi Hydrogen, University of Wisconsin Press, 'Madison,Wisconsin, 1937) failed in attempting to selectively hydrogenate thecarbonyl group of alde hydes and ketones which also contained olefinicdouble bonds. Now, however, we have discovered an effective techniquefor the selective hydro-v genation of carbonyl groups in certaincarbonylolefin combinations.

In one embodiment of our invention, we have succeeded in preparingalcohols and highermolecular weight olens from a mixture of secondaryolens and tertiary olens, by a combination process including anacid-copolymerization step, a treatment with carbon monoxide andhydrogen according to the so-called Oxo process, and our selectivehydrogenation technique. A mixture of n-butyl'ene and isobutylene, forexample, may be copolymerized with sulfuric acid to give a mixture ofisooctenes, the isooctenes are then reacted with carbon monoxide andhydrogen by means of the carbonylation step of the Oxo process,

I l -(2=+ CO H3 Cf|3 oHo to give a mixture of nonyl aldehydes andisooctenes, and the resulting mixture is then contacted with hydrogen inthe presence of a cobalt catalyst at elevated temperature and pressure,the aldehydes being thereby converted into the corresponding nonylalcohols,

l---l-H CHO Onion and the isooctenes remaining unaiected` The selectivehydrogenation step of our invention offers the important advantage thatit avoids the necessity of isolating the aldehydes `from thecanbonylation product of the Oxo process, an operation that is known toresult in large losses of aldehydes through aldol condensation and other`undesired reactions. Our selective hydrogenation step also avoids theheat effects that would be produced if the olefins `were reduced toparaliins in the same operation, and the problem of temperature controlwithin the reactor is thereby made less diflicult. Our selectivehydrogenation step has the additional important advantage that itpermits the recovery and utilization or recycling of non-carbonylatedolens, which would be converted to parains inthe conventionalhydrogenation procedure.

One object of our invention is to provide 'a means for convertingcarbonyl compounds into alcohols in the presence of olenic dou-blebonds, Without simultaneously saturating the double bonds. Anotherobject of our invention is to provide a means for hydrogen'atingcarbonyl compounds resulting from the carbonylation step of the Oxoreaction, while simultaneously leaving non-carbonylated olenicconstituents unaffected, so that the latter may be recycled to the lcarbonylation step. IOther objects of our invention, and its advantagesover the prior art, will be apparent from the following description andexamples.

Our process is especially suitable for the selective hydrogenation ofthe products resulting from the carbonylation of secondary olefin-tentiary olen copolymers, such as copolymers of mixtures containing atleast one olen from the group comprising propylene, l-butene, Z-butene,and secondary amylenes, and at least Vone olen from the group comprisingisobutylene, 2-methyl-l-'butena and Z-methyl-Z-butene. Thus, our processAis suitable for treating the mixture of nonyl aldehydes and isooctenesobtained from n-butylene-isobutylene codimer, the `mixture of octylaldehydes and isoheptenes obtained from propylene-isobutylene copolymer,the mixture of nonyl aldehydes and isooctenes obtained from prop yleneand 2-'methylbutenes, vthe mixture of decyl aldehydes and isononenesobtained from secondary amylenes and isobuty'lene, the mixture ofundecyl aldehydes and isodecenes obtained from secondary amylenes and aZ-methylbutene, and similar mixtures of aldehydes and olens.

The copolymerization of olefin mixtures lmay be effected by variousprocesses, most of which employ acidic catalysts, such as sulfuric acid,phosphoric acid, or hydrogen fluoride; `or 2potentially acidic catalystssuch as copper pyrophosphate or boron fluoride; or ,solid tcatalystssuch as silica-alumina or acid-treated bentonite. Hot sulfuric acid, forexample, absorbs both secondary and tertiary olefins at temperaturesaround 140-194 F. and converts them into copolymers, comprising chieythe various isomeric dimers. In a particularly successfulcopolymerization process, secondary butylenes and isobutylene are passedover a solid granular catalyst, comprising phosphoric acid adsorbed onclay or other inert material, at 350-500c F. and around 40 atmospheres.Under these conditions, when the charge stream contains 30% of secondarybutylenes and 15% of isobutylene, approximately 67% of the olens areconverted into a product, of which 85% is dimer and 15% is trmer.Fractional distillation of the crude product yields a dimer fractionhaving properties and composition as in the following illustrativeexample:

Butylene-Isobutylene Codimer: Properties and Total isooctene content,percent Over 98. Distribution of isooctenes, percent by weight:

2,2,3-trimethylpentenes 21 2,2,4-trimethylpentenes 10.2,3,3-trimethylpentenes 11. 2,3,4-trimethylpentenes 47. Dimethylhexenes10.

The resulting mixture may be subjected to carbonylation by contact witha mixture of hydrogen and carbon monoxide having a molar ratio betweenabout 0.5:1 and 5:1 at a temperature between about 200 and 500 F., apressure between about 50 and 300 atmospheres, and a liquid spacevelocity between about 0.05 and 10 per hour, in the presence of acatalyst comprising cobalt or iron, as disclosed in the copending jointapplication of Donald E. Burney and Bernard H. Shoemaker, Serial No.788,845, filed November 29, 1947, now U. S. Patent No. 2,628,981. Underthese conditions, between 20 and 60 percent of then-butylene-isobutylene codimer is converted into nonyl aldehydes, plus aminor proportion of nonyl alcohols, in a reaction time between about 30and 120 minutes.

We have now found that mixtures of aldehydes and olens, such as thoseproduced by the reaction of secondary olefin-tertiary olen copolymerswith carbon monoxide and hydrogen in the Oxo process, may be selectivelyhydrogenated over a cobalt catalyst at an elevated pressure, suitablyabove about 500 pounds per square inch and preferably below about 4000pounds per square inch, a temperature between about 150 and 700 F., anda liquid space velocity between about 0.1 and 5.0 volumes of chargingstock per volume of reaction zone per hour, the aldehydes being therebyconverted into the corresponding alcohols, without the simultaneoussaturation of any substantial proportion of the olefinic compounds inthe charging stock. The hydrogenation may be carried out in conventionalbatchtype autoclaves; or the liquid charging stock may be passed upwardconcurrently with hydrogen through a continuous reactor in contact withthe catalyst, suitably at a temperature between about 350 and 600 F.; orthe liquid charging stock may be passed as a continuous phase downwardthrough a. reactor countercurrent to the hydrogen. In the preferred formof our invention, the mixture of olefin and carbonyl compound istrickled downward over a granular or pelleted catalyst in a continuousatmosphere of hydrogen at a temperature between about 350 and 600 F., apressure between about 500 and 1500 pounds per square inch, and a liquidspace velocity between about 0.2 and 2.0 per hour.

Catalysts comprising cobalt as the active con stituent are suitable forthe selective hydrogenation reaction of our invention. Pure cobalt maybe used as the catalyst in finely divided form, or in the form ofgranules, fragments, or shaped masses having finely divided surfaces; orthe meta1 may be supported on powdered, pelleted, or granular inertcarriers, such as silica, bonded silica (for example, Filtros), pumice,alumina, Carborundum, glass kieselguhr, and the like; and it may becombined with various promoters, such as thoria, magnesia, and the like.We prefer to use supported catalysts containing between about 5 and 15per cent cobalt, but the proportion of cobalt is not a critical variablein our process.

Freshly prepared cobalt catalysts, when first used in our process, maysometimes exhibit a tendency to hydrogenate both the carbonyl groups andthe olenic double bonds of our charging stock. However, in such cases,we have found that the activity of the catalyst toward olefnic doublebonds is lost very rapidly during exposure to the charging stock andoperating conditions of our process.

Prior to the hydrogenation step, the liquid product from thecarbonylation step of the Oxo process should preferably be treated toremove substantially all cobalt carbonyl and carbon monoxide therefrom,since it is known that carbon monoxide tends to retard thehydrogenation. The purification may be accomplished, for example, bypurging the liquid with hydrogen or an inert gas, or by washing theliquid successively with an acid and with water.

For the same reason, the hydrogen that is supplied to the hydrogenationreactor should preferably contain less than about 2 percent of carbonmonoxide, and should be substantially free from catalyst poisons such ashydrogen suldc and the like.

After the Y selective hydrogenation has been completed, the reactionproduct contains alcohols, olefins, and a small proportion of saturatedhydrocarbons. This mixture may be separated by techniques that are wellknown in the art. For example, the alcohols will ordinarily besubstantially higher-boiling than the hydrocarbon constituents; thehydrocarbons may therefore be distilled out, and may be recycled to thecarbonylation step in whole or in part, if desired: and the remainingalcohols may then be subjected to further purification by fractionaldistillation. Alternatively, the alcohols may be selectively extractedfrom the reaction product, suitably by use of an extractant mediumcomprising a glycol, a lower aliphatic alcohol, or a hydroxy ether. Or,the reaction product may be subjected to extractive distillation with asuitable solvent such as a member selected from the groups named above,the hydrocarbon constituents being thereA by removed as an overheadfraction. AS a :Ellic-A ther alternative, the reaction mixtures may besubjected to an esterification procedure, suitably with boric acid,phthalic anhydride, or the like, in order to convert the alcoholstherein to the corresponding esters, and the hydrocarbon constituentsmay then be conveniently distilled out. The esters may afterwards beseparated and used as such, or may be hydrolyzed to regenerate thealcohols. These constitute particularly advantageously embodiments ofour invention, since the selective-hydrogenation step permits therecycle oi unreacted olens to the carbonylation step, whereas in theusual hydrogenation procedure they would become saturated anduns-uitable for recycling. As a still further alternative, the entirereaction product may be subjected to dehydration, suitably in the vaporphase at around TO-900 F. and one atmosphere over an alumina catalyst,in order to reconvert the alcohols therein to oleflns having one morecarbon atom than the olens in the charging stock prior to thecarbonylation reaction,

Prior to either the carbonylation step or the selective hydrogenationstep, we may optionally add to the liquid charging stock an inert liquidas a diluent and as a mutual solvent for the reactants and reactionproducts. As illustrations of such liquids, the following may be cited:aliphatic, aromatic, and naphthenic hydrocarbons; others; and alcohols,in particular the lower aliphatic alcohols, benzyl alcohol,tetrahydrofurfuryl alcohol, and the like.

Figure 1 illustrates an embodiment of our invention employing batch-typeequipment. An olen copolymer charging stock is supplied through line IIto mixing and metering tank I2 equipped with agitator I3, wherein aquantity of powdered catalyst, suitably 3 to 5% of cobalt on kieselguhr,is suspended in `the liquid. The susl pension is withdrawn through lineI4 by pump I 5 and delivered through heat exchanger vI6 into reactor II.A now of gases is maintained through the reactor during the llingoperation at a rate sufficient to maintain the solid catalyst insuspension, and the liquid charge may be recirculated from the bottom ofreactor I'I through heat exchanger it by way oi line I8, valve I9, andpump I5 in order to bring the charge up to reaction temperature,optimally around 350 F. When the desired liquid level is reached in thereactor, the vessel is closed and a mixture of carbon monoxide andhydrogen in approximately 1:1 molar ratio is introduced through line 20,compressor 2l, and sparger lines 22 until the pressure reachesapproximately 200 atmospheres, From the top of the reactor, gas emergesthrough cooler 23 and is expanded through valve 24 into separator 25,:from which a portion is purged through valve 20 as required to preventexcessive build-up of non-reactive gases, and the remainder is recycledthrough valve 21 and compressor 2l to the reactor. The recycle andmakeup gases ordinarily have a temperature below about 100 F., and aredistributed to various points in the reactor, as indicated in thedrawing, to maintain an approximately uniform temperature.

After the reactive components of the olefin copolymer have reacted tothe desired extent with carbon monoxide and hydrogen, the supply of gasto compressor 2| is stopped, and the gas remaining in the system isreleased through purge valve 2B. The reactor contents are adjusted to atemperature between about 375 and 425 F. by withdrawingr a stream. ofthe reaction mixture through cooler 2,8 .and recycling it through valve.29, pump I5, and heat exchanger It. Hydrogen, substantially free fromcarbon monoxide, is then introduced into the reactor through line 20 andcompressor 2 I, and is purged through valve. 2.3 until the systemcontains little or no carbon monoxide. The hydrogen pressure is thenraised to between about 500 and 1500 pounds per square inch, andhydrogen is recycled through cooler 23, valve 24, separator 25, valve2^?, compressor 2|, and sparger lines 2 2 to the reactor to maintain thecatalyst in suspension and to help in controlling the reactiontemperature. Under the described conditions,y the reduction of aldehydesto alcohols takes place readily,

with little or no reduction of oleiins that failedto react with carbonmonoxide and hydrogen in the carbonylation step. When the hydrogenationhas been completed, the supply of hydrogen is stopped, the pressure isreleased through valve 26 to approximately 5 or 10 atmospheres, and thereactor charge is forced by the residual pressure through cooler 2.8,valve 30, separator 25, valve 3I, and filter 32, where the suspendedcatalyst is removed. The recovered catalyst may be washed from thefilter through line 33, suitably with filtered product, and subsequentlyreused. The filtered product is withdrawn through line 34 and subjectedto further process steps, such as fractional distillation (apparatus notillustrated) to separate the various components thereof.

Figure 2 illustrates a continuous process for carrying out ourinvention.

An olen charging stock, supplied through line Ii I, is introduced bypump II2 through heat exchanger II3 into the top of carbonylationreactor l I4, where it is contacted at a pressure be,` tween about and300 atmospheres, preferably about 200 atmospheres, and a temperaturebetween about 200 and 500 F., preferably between about 32,5 and 375 F.,with an equimolar mixture 0f carbon monoxide and hydrogen, introducedthrough line II5 and compressor III. The rate of injection of copolymeris suitably between about 0.05 and l0 volumes per hour per unit volumeof reaction zone, and preferably between about 0.5 and 2 per hour. Thereactor is packed with a suitable carbonylation catalyst, such asmetallic cobalt supported on an inert siliceous. material, arranged insuch manner that efcient contact is obtained between the liquidhydrocarbon and the reactant gases. Makeup catalyst, suitably metalcarbonyls, such as cobalt or iron carbonyl, or oil-soluble organicacidsalts, such as iron or cobalt stearato or' naphthenate, may be addedthrough line Ill to` the oleiin stream in line III, in order tocompensate for any loss of catalyst from the reactor as dissolvedcarbonyl or entrained solids in the product stream. Alternatively, solidcatalyst may be omitted from the reactor altogether, and the totalcatalyst requirements may be supplied with the charging stock in theform of metal carbonyls (suitably between about 0.1 and .2 percent byWeight) or metal salts of organic acids (suitably between about 0.1 and10 percent by weight). The processed liquid stream and the unreactedgases are withdrawn from the base of the reactor through line IIB tohigh-pressure separator II9.

The gas stream from separator H2 flows through Valve I2!! and cooler I2Iinto low-pressure separator 122, where condensed liquids are removed.The gas stream emerging from sepa 7 arator |22 through line |23 isdivided, part of it flowing through valve |24 to compressor ||6, fromwhich it is recycled to reactor I |4, and the remainder being purgedthrough line |25, or sent to suitable gas reprocessing equipment.

The liquid stream from separator ||9 ows into cooler |26, and is dividedinto two streams. One stream is recycled through valve |21, pump |28,line |29, and heat exchanger ||3 to reactor |14, where it serves toregulate the temperature of the exothermic reaction between the olefinstream, hydrogen, and carbon monoxide. The rate of recycle may beadjusted to maintain the desired temperature, the cooling liquid beingintroduced at the top of the reactor or at such points within it as maybe required to control localized heating. The remainder of the liquidstream from cooler |26 ows through valve |30 to low-pressure separator|3|, where the liquid is freed of dissolved gases. The gases arecombined in line |23 with the gases from separator |22.

The liquid streams from separators |22 and |3| are combined andtransferred by pump |32 through line |33 and heat exchanger |34 intoselective hydrogenation reactor |35. This liquid comprises a mixture ofaldehydes and unreacted olens, together with minor proportions ofalcohols and saturated hydrocarbons, and it ordinarily contains minorproportions of the catalyst from the carbonylation reaction, in the formof the metal carbonyl, oil-soluble metal salts, or suspended solids. Thecatalyst may be removed, if desired, before the liquid is introducedinto reactor |35. For example, the liquid stream may be treated withhydrogen or other inert gases at elevated temperatures, suitably aboveabout 150 F., in order to destroy metal carbonyl and to strip out theliberated carb-on monoxide, and the precipitated metal may then beremoved by filtration or centrifugation; or the liquid stream may bescrubbed with a dilute acid, such as sulfuric acid, and then with water(apparatus not shown). The hydrogenation reactor |35 contains aselective hydrogenation catalyst comprising cobalt as the 'activecomponent, preferably on an inert support, such as Filtros (a bondedsilica), or pumice. Hydrogen, preferably containing not more than about2 percent of carbon monoxide is supplied by compressor' |56 through line|31 into the bottom of reactor |35. The hydrogen passes upward throughthe downwardflowing liquid stream, the pressure within the reactor beingmaintained around 800 pounds per square the temperature around 550 F.Under these conditions, the aldehydes are converted into alcohols, whilethe olefins are substantially unaiected. Excess hydrogen is withdrawn atthe top of reactor |35 through valve |33 and cooler |39 intolow-pressure separator |40, from which the gas phase is withdrawn andpurged through line Uil to prevent the accumulation of inertconstituents within the reactor; or the gas phase may be recycled Whollyor in part to gas processing equipment, not shown.

From the bottom of reactor |35, the selectively hydrogenated liquid iswithdrawn through cooler |42, and the stream is then divided, part of itbeing recycled through valve |43, pump IM, line |33, and heat exchanger|34 to reactor |35 for use in regulating the reaction temperaturetherein at the desired level, while the remainder of the liquid streamfrom cooler |42 is reduced in pressure to around one atmosphere throughvalve |45 and allowed to flow into low-pressure separator |46, fromwhich the dissolved gases are removed and purged or recycled as desired.

The liquid streams from separators |4|l and |46 are combined andtransferred to a fractionation system, where the hydrocarbons andalcohols may be segregated and purified. For this purpose, Figure 2illustrates a two-stage fractionation method:

The liquid streams from separators |550 and |46 are transferred by pump|41 through heater |48 into fractionating column |49 at an intermediatepoint. The hydrocarbon constituents, being lower boiling than thealcohols, are fractionally distilled overhead through condenser |59 intoseparator |5i, from which a portion is reuxed through valve |52 to thetop of column |49, and the remainder is withdrawn through valve |53 tostorage, or to further purification. The hydrocarbon stream, comprisingmainly olens, may be recycled to reactor le, either with or without anintermediate purification stage. In the event that recycling isemployed, a small proportion of the recycle stock is preferablywithdrawn from the process in order to prevent the accumulation thereinof saturated constituents and other constituents which will not undergothe carbonylation reaction.

The bottoms stream from column |49 is transferred by pump |54 throughheater |55 into fractionator column |56 at an intermediate point. Thealcohols are fractionally distilled overhead through condenser |51 intoseparator |58, from which a portion is refluxed through valve |59 to thetop of column |56, and the remainder is withdrawn through valve |55 tostorage or further purification. A small quantity of higher-boilingmaterial is withdrawn from the bottom of fractionator |56 through cooler|6|.

1t will be noted that reactor H4 is shown with liquid and gas flowingconcurrently downward, Whereas in reactor |55 the liquid stream flowsdownward countercurrent to the gas stream. It is intended that either ofthese flow systems may be used in either reactor. Moreover, a thirdmodification, in which the liquid and gas flow upward in parallel, mayalso be used in either reactor.

The following specic examples will more fully illustrate our invention.

Example I A solution of cobalt nitrate was prepared by mixing 120 gramsof the hexahydrate (ce (No3) 2.61120) with 50 milliliters of water andheating nearly to boiling. To the hot solution were added T grams of 4-8mesh Filtros (a bonded silica), and the mixture was stirred continuouslyand heated until substantially all of the water had evaporated. In thisway, the cobalt nitrate was deposited uniformly on the Filtros. Theheating was then continued, and the cobalt nitrate was decomposed intocobalt oxide, as evidenced by the evolution of red fumes of nitrogenperoxide. After the evolution of red fumes had ceased, the material wascooled and screened to remove the nes. The oxide Was then reduced withhydrogen at atmospheric pressure and 700 F. for five hours. A yield of192 grams of catalyst containing 5.4 percent cobalt was obtained. Afterreduction, the catalyst was handled under an inert atmosphere.

A charging stock was prepared by contacting a n-butylene-isobutylenecodimer with carbon n'onoxide and hydrogen according to the carbonylation step of the Oxo process. The resulting product, containing 34percent by volume of nonyl aldehydes, 8 percent nonyl alcohols, 516 per-1G EampleIII An x0-process carbonylation-step reaction product, preparedfrom a n-butylene-isobutylene codimer, and containing 24 percent byvolume cent isooctenes, and .2 percent high-boiling ma- 5 of .nonylaldehydes 7 percent Yrmnyl alhols terials, was trickled downward at therate of 209 55 rpercent sooctenes, and 9 percent high boilers, m1. perhour through a reactor having Yarl ill-51de was trickled downward over645 milliliters of diameter of 1.5 inches and a catalyst zone packed 4 8mesh AFiltros, mpregnated with approxi with cobalt catalyst, prepared asdescribed ,aboveg mately 4 9 percent of reduced cobalt according t0 adepth 0f 2-5 feet 'A temperature of 380A@ w to the general procedureoutlined in Example l F. and a hydrogen pressure of 7750-856 pounds Thereacton conditions were as follows: per square inch were maintained inthe reactor. a After two passes over the catalyst V(equivalent toTemperature Catalyst mldsectlOL 609g E 2 a. space velocity of0.115/hr.), the product COH- Hydrogen praSSure--`*^- 800 1b/m" sisted of35 percent by Volume nonyl alcohols, 3.5 15 Feed rate------n-W 492mL/hr' percent nonyl aldehydes, 50 percent hydlocal'- Space Velocltyhquld M (L8/hr' bons having a bromne number 0f 134, 'COlT- On fractionaldistillation, the product was :found sponding to an unsaturation ofover` 90 percent, to contain 34 pel-Cent .nonyl alcohols', correspondandthe remainder high-.boiling materials. ing ,to 38 percent conversion ofthe aldehydes Example II originally present, 3 percent nonyl aldehydes,47 percent hydrocarbons having a bromine A hydrogenation reactor havingyan inside Ad1 number of 132 Corresponding to 96 percent un ameter of1.5 inches and a reaction Zone 25 saturation andpercent high boilers.inches in length was charged with 645 milliliters of unreduced cobaltoxide catalyst, prepared as Example IV described in Example I, and `thecatalyst was .A series of selective hydrogenation experi- IeduCed inplace With hydrogen at aIOund 800 ments was carried out on a chargingstock con F. for six hours. taining `2,1 percent by volume of nonylalde- A Il-butyleIlS-sobutylehe @Odimr having a hydes, 7 percent nonylalcohols, 60 percent `isobI'OmIlS number 0f 137 `WaS subjected O CalbOh-30 octenes, 7 percent high ,boiler-s, and 0 6 mg, S01- ylaton under OXOprocess Conditions, and a uble cobalt compounds per milliliter, that hadproduct was obtained consisting of 21 percent been prepared byContacting a n buty1ene is0 by volume of nonyl aldehydes, 7 percent1101134 butylene codimer with carbon Vmonoxide and alCOhOlS, 65 percentSOOGteIleSy and 7 'percent hydrogen under 0x0-process carbonylation-stephigh-boiling materials- The CalbOIlyatGnDrOdconditions. 'Thecarbonylat'ion product was uct Was fed HO '611612010 0f thelllydiogenation trickled downward over 645 milliliters Aoi .ll-8 IEBJCOIat a rate Of 193 milliliter-S per 110111 and mesh Filtros, 'impregnatedwith approximately contacted with hydrogen and cobalt catalyst at 4.9percent of reduced cobalt according to the about 415 F. and 800 poundsDer square inch. general procedure outlined in Example I, and Thereactor effluent was Cooled, flashed 170 at- 40 contained in a, zonemeasuring 25 inches in mospheric pressure, and fractionally distilledlength in a hydrogen-filled reactor having an under reduced pressure.The product consisted inside diameter of 115 inches. of 27 percent byvolume of nonyl alcohols, 2 The experiments were continued for one hourpercent nonyl aldehydes, 63 percent hydrocarat each set of reactionconditions before the bons having a bromine number of 137, correproductWas collected for evaluation, Analysis sponding to 100 percentunsaturation, and 8 of the liquid products was by fractionaldistilpercent high-boiling materials. Thus, 90.5 perlation. The reactionconditions and results were cent of the aldehydes had been reduced tothe as follows:

Product composition Hydrogen Feed Space sicognfle- Pressure, Tgrp" rate,vvmtty Alcc- AldevHydro- H'igh hydes to lb./1n.2 ml./hr. ,1g 1, hols,hydes, cartoons, boilers, alcohols, vol. vol. vol. vol. percent percentpercent Apercent percent 415 19s 0.a 27 2 5s s o1 405 363 o. 6 27 .5 6o5 ve 402 54o o. s 19 11 63 i 4s 505 51o os so 2 so 2 91 557 o as 29 2`to 5 91 corresponding alcohols, while the oleiins were Brominetitration of the hydrocarbon fractions unchanged. of the productsindicated that all of them were When a similar n-*butylene-isobutylenecodibetween.96 and 100 percent oleiinic. mer which had not beensubjected to carbonyl- *Example V ation was fed at a rate of 192milliliters per hour into the same reactor, containing the same AnOXO-process carbonylation-step reaction catalyst, and contacted withhydrogen at Soo product prepafed from al; Il-butyleILe-.sobutylpoundsper square inch and an average temperen@ Codlme and Contammg 17 Percentby ature of 396 F., the product was 100 percent Volume 0f IIODYIaldehydes, 7 Percent DOIlyl al- Cs hydrocarbons having a bromine numberof cohols, 71 percent isooctene, and 5 percent high 5, which indicatedthat 96 percent of the olens bOlerS, Was passed llDWald through 645milli- Originauy present in the codimer had been hylitcrs of 4-8 meshFiltros, impregnated with 4.9 drogenated to the corresponding parains.75 Weight percent of reduced cobalt, in a reactor having an insidediameter of 1.5 inches and a catalyst bed 25 inches in length. Thereaction conditions were as follows:

Temperature, catalyst mid-section-. 550 F.

Hydrogen pressure 800 lb./in2. Excess hydrogen rate 1.0 ft.3/hr. Feedrate 323 ml./hr. Space velocity, liquid 0.5/hr.

Example VI A propylene-butylene copolymer was fractionally distilled,and from it was separated a C7 fraction having a bromine number of 158.The C7 fraction was mixed with 0.1 percent by weight of cobalt in theform of cobalt tallate, and the resulting solution was subjected tocarbonylation by contact with a 1: 1 mixture of carbon monoxide andhydrogen at 325 to 250 F., 3000 pounds per square inch, a liquid spacevelocity of (L5/hour, and an excess gas rate of 200 percent of thetheoretical quantity necessary for complete carbonylation. Theconversion was 52 percent, molar basis, of the C7 olens, yielding aproduct having the following composition:

Mole-percent C7 hydrocarbons (Br No., 130.4) 48 Cc aldehydes 36 Caalcohols l2 Bottoms 4 The total product liquid was washed at 80 F. with25 percent by volume of aqueous 5% sulfuric acid, then twice with thesame proportion of water. The washed product liquid was steamdistilled,and all of the organic materials except the bottoms were withdrawnoverhead as a distillate fraction. The distillate fraction was passeddownward over a reduced 12 percent cobalt-on-pumice catalyst at 375 F.,3000 pounds per square inch, and a liquid space velocity of derstoodthat we do not wish to be limited to the specific charging stocks andoperating conditions described therein, since our invention is broadlyapplicable, as defined elsewhere in the specification. In general, itmay be said that any modications or equivalents that would ordinarilyoccur to those skilled in the art are to be considered as lying withinthe scope of our invention.

The products of our invention are alcohols of a wide range of chemicaland physical properties. They are useful as solvents and as ingredientsof hydraulic uids, and are capable of being converted into a widevariety of chemical derivatives. For example, they may be oxidized toaldehydes and carboxylic acids; they may be reacted with ammonia to formamines, and with other amines to form secondary and tertiary mixedamines; they may be dehydrated to form olens and ethers; they may beused to alkylate aromatics; and they may be converted by conventionalmethods into esters. Especially useful esters may be prepared from themixed octyl alcohols obtainable from propylene-butylene copolymers andfrom the mixed nonyl alcohols obtainable from n-butylene-isobutylenecodimer according to our invention. Among such esters may be cited thephthalates, phosphates, sebacates, adipates, stearates, citrates, andthe like, which are useful as plasticizers for numerous plastics,elastomers, and resins, including vinyl polymers, butadiene-styrenerubbers, and cellulose plastics; the sulfates, which are useful aswetting agents; and the acrylates and methacrylates, which, after beingpolymerized, are excellent viscosity index improvers for lubricatingoils.

This application is a continuaticn-in-part of our application Serial No.788,847, filed November 29, 1947, now abandoned.

In accordance with the foregoing specication, we claim as our invention:

1. In a process for selectively hydrogenating aldehydes in a mixturecontaining aldehydes and olens obtained by subjecting a secondaryolefin-tertiary olefin copolymer to reaction with carbon monoxide andhydrogen, the step which comprises contacting said mixture with hydrogenat a temperature between about and 700 F. an elevated pressure aboveabout 500 pounds per square inch, and a liquid space velocity betweenabout 0.1 and 5.0 volumes of charging stock per Volume of reaction zoneper hour in the presence of a cobalt catalyst.

2. The process of claim 1 wherein said catalyst consists essentially ofmetallic cobalt and an inert carrier.

3. The process of claim 1 wherein said copolymer is a copolymer of anolefin selected from the group consisting of prcpylene, 1-butene,2-butene, and the secondary amylenes, and an olefin selected from thegroup consisting of isobutylene, 2- methyl-l-butene, andZ-methyl-Z-butene.

4. In a process for selectively hydrogenating aldehydes in a mixturecontaining aldehydes and oleiins obtained by subjecting a secondaryolefin-tertiary olen copolymer to reaction with carbon monoxide andhydrogen, the step which comprises contacting said mixture with hydrogenat a temperature between about 150 and 700 F., an elevated pressurebetween about 500 and 4000 pounds per square inch, and a liquid spacevelocity between about 0.1 and 5.0 volumes of charging stock per Volumeof reaction zone per hour in the presence of a cobalt catalyst.

5. The process of claim 4 wherein said copolymer is a propylene-butylenecopolymer.

6. The process of claim 4 wherein said copolymer is an-butylene-isobutylene codimer.

7. In a process for selectively hydrogenating aldehydes in a mixturecontaining aldehydes and olens obtained by subjecting a secondaryolefin-tertiary olefin copolymer to reaction with ,A carbon monoxide andhydrogen, the step which comprises passing said mixture downward over asupported cobalt catalyst in an atmosphere of hydrogen at a temperaturebetween about 350 and 600 F., a pressure between about 500 and 4000pounds per square inch, and a liquid space velocity between about 0.2and 2.0 volumes of i3 charging stock per volume of catalyst zone perhour.

8. In a process for the preparation of alcohols from a secondaryolefin-tertiary olen copolymer. the steps which comprise subjecting saidcopolymer to reaction with carbon monoxide and hydrogen in acarbonylation zone, contacting the resulting product with hydrogen at anelevated pressure between about 500 and 4000 pounds per square inch, ata temperature between about 150 and 700 F., and a liquid space velocitybetween about 0.1 and 5.0 volumes of charging stock per volume ofreaction zone per hour in the presence of a cobalt catalyst, separatingalcohols and unreacted olens from the resulting product, and recyclingpart of said unreacted olens to said carbonylation zone.

9. In a process for selectively hydrogenating aldehydes in a mixturecontaining nonyl aldehydes and isooctenes obtained by subjecting a 20n-butylene-isobutylene codimer to reaction with carbon monoxide andhydrogen, the step which comprises contacting said mixture with hydrogenat a pressure between about 500 and 4000 pounds per square inch, atemperature between about 350 25 and 600 F., and a space velocitybetween about 0.2 and 2.0 volumes of liquid per volume of reaction zoneper hour in the presence of a cobalt catalyst.

10. In a process for selectively hydrogenating aldehydes in a mixturecontaining octyl aldehydes and isoheptenes obtained by subjecting apropylene-isobutylene copolymer to reaction with carbon monoxide andhydrogen, the step which comprises contacting said mixture with hydrogenat a pressure between about 500 and 4000 pounds per` square inch, atemperature between about 350 and 600 F., and a space velocity betweenabout 0.2 and 2.0 volumes of liquid per volume of reaction zone per hourin the presence of a cobalt catalyst.

DONALD E. BURNEY. WILLIAM J. CERVENY.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,327,066 Roelen Aug. 17, 1943 2,414,276 Sensel et al Jan. 14,1947 2,437,000 Gresham et al Mar. 9, 1948 2,464,916 Adams et al Mar. 22,1949

1. IN A PROCESS FOR SELECTIVELY HYDROGENATING ALDEHYDES IN A MIXTURE CONTAINING ALDEHYDES AND OLEFINS OBTAINED BY SUBJECTING A SECONDARY OLEFIN-TERTIARY OLEFIN COPOLYMER TO REACTION WITH CARBON MONOXIDE AND HYDROGEN, THE STEP WHICH COMPRISES CONTACTING SAID MIXTURE WITH HYDROGEN AT A TEMPERATURE BETWEEN 150 AND 700* F. AN ELEVATED PRESSURE ABOVE ABOUT 500 POUNDS PER SQUARE INCH, AND A LIQUID SPACE VELOCITY BETWEEN ABOUT 0.1 AND 5.0 VOLUMES OF CHARGING STOCK PER VOLUME OF REACTION ZONE PER HOUR IN THE PRESENCE OF A COBALT CATALYST. 